2-trifluoromethylbenzimidazoles

ABSTRACT

BENZIMIDAZOLE COMPOUNDS OF THE FORMULA:   2-X,4-R1,5-R2,6-R3,7-R4-BENZIMIDAZOLE   AND SALTS THEREOF, WHERE IN THE ABOVE FORMULA R1, R2, R3 AND R4 MAY BE THE SAME OR DIFFERENT AND ARE SELECTED FROM THE GROUP COMPRISING HYDROGEN, ALKYL (FOR EXAMPLE 1-6 CARBON ATOMS SUCH AS METHYL, ETHYL OR PROPYL), HYDROXY, ALKOXY (FOR EXAMPLE METHOXY, ETHOXY OR BUTOXY), NITRO, HALOGEN (FOR EXAMPLE CHLORO, BROMO OR FLUORO), PSEDUOHALOGEN (FOR EXAMPLE CYANO, THIOCYANO, ISOTHIOCYANO OR AZIDO), SUBSTITUTED ALKYL (FOR EXAMPLE, TRIFLUOROMETHYL, CHLOROMETHYL, BROMETHYL, TRICHLOROMETHYL, HYDROXYMETHYL, 2-CHLOREETHYL, 2-HYDROXYETHYL OR 2-METHOXYETHYL), CARBOXY, CARBOXY ESTER, CARBOXY AMIDE, N-SUBSTITUTED CARBOXY AMIDE, N-DISUBSTITUTED CARBOXY AMIDE, AMINO (FOR EXAMPLE METHYLAMINO, DIMETHYLAMINO, ACETYLAMINO, TRIFLUOROACETYLAMINO, BENZENESULPHONAMIDO, PARATOLUENESULPHONAMIDO, METHANESULPHONAMIDO), THIOL, ALKYLTHIOL, AND OXYGENATED DERIVATIVES THEREOF (FOR EXAMPLE -SOR5 OR -SO2R5 WHERE R5 IS ALKYL), SULPHONIC ACID AND ESTERS AND AMIDES THEREOF, SUBSTITUTED AMIDE (FOR EXAMPLE, PHENYLSULPHAMYL, ETHYLSULPHAMYL, CHLOROETHYLSULPHAMYL), RADICALS AND WHERE X IS TRIFLUOROMETHYL OR PENTAFLUOROETHYL, POSSESS PHYSIOLOGICAL ACTIVITY AND ARE USEFUL IN THE FORMULATION OF PHYSIOLOGICALLY ACTIVE COMPOSITIONS.

United States Patent Int. Cl. C07d 49/38 US. Cl. 260309.2 ClaimsABSTRACT OF THE DISCLOSURE Benzimidazole compounds of the formula:

and salts thereof, where in the above formula R R R and R may be thesame or different and are selected from the group comprising hydrogen,alkyl (for example 16 carbon atoms such as methyl, ethyl or propyl),hydroxy, alkoxy (for example methoxy, ethoxy or butoxy), nitro, halogen(for example chloro, bromo or fluoro), pseudohalogen (for example cyano,thiocyano, isothiocyano or azido), substituted alkyl (for example,trifluoromethyl, chloromethyl, bromoethyl, trichloromethyl,hydroxymethyl, 2-chloroethyl, 2-hydroxyethyl or Z-methoxyethyl),carboxy, carboxy ester, carboxy amide, N-substituted carboxy amide,N-disubstituted carboxy amide, amino (for example methylamino,dimethylamino, acetylamino, trifl-uoroacetylamino, benzenesulphonamido,paratoluenesulphonamido, methanesulphonamido), thiol, alkylthiol, andoxygenated derivatives thereof (for example -SOR or SO R where R isalkyl), sulphonic acid and esters and amides thereof, substituted amide(for example, phenylsulphamyl, ethylsulphamyl, chloroethylsulphamyl),radicals and where X is trifluoromethyl or pentafluoroethyl, possessphysiological activity and are useful in the formulation ofphysiologically active compositions.

This application is a continuation-in-part of application Ser. No.476,185, filed July 30, 1965, now abandoned, which application in turnis a continuation-in-part of application Ser. No. 343,225, filed on Feb.7, 1964, now abandoned.

The present invention relates to certain substituted benzimidazoleswhich have been found to possess physiological activity.

It has been found that the substituted benzimidazoles as hereinafterdescribed are active in many fields and that certain members are highlyactive as herbicides, insecticides, molluscicides and fungicides.

3,795,680 Patented Mar. 5, 1974 ice Accordingly the present inventionrelates to substituted benzimidazole compounds of the following formula:

(hereinafter called Formula I) and salts thereof, where in the aboveformula R R R and R may be the same or different and are selected fromthe group comprising hydrogen, lower alkyl (for example 1-6 carbon atomssuch as methyl, ethyl or propyl), hydroxy, lower alkoxy (for examplemethoxy, ethoxy or butoxy), nitro, halogen (for example chloro, bromo orfluoro), pseudohalogen (for example cyano, thiocyano, isothiocyano orazido), substituted alkyl (for example trifluoromethyl, halo loweralkyl, chloromethyl, bromomethyl, trichloromethyl, hydroxymethyl,2-chloroethyl, 2-hydroxyethyl or Z-methoxyethyl), carboxy, carboxyester, carboxy amide, N-substituted carboxy amide, N-disubstitutedcarboxy amide, amino or monoor disubstituted amino (for examplemethylamino, dimethylamino, acetylamino, trifiuoroacetylamino,benzenesulphonamido, paratoluenesulphonamido, methanesulphonamido),thiol, alkylthiol, and oxygenated derivatives thereof (for example 4016or SO R where R is alkyl), ,sulphonic acid and esters and amidesthereof, substituted amide (for example phenylsulphamyl, ethylsulphamyl,chloroethylsulphamyl), radicals and where X is trifiuoromethyl orpentafluoroethyl.

The present invention also provides the salts of the substitutedbenzimidazoles of the formula indicated above as new compounds. Forpurposes of this invention the salts are the equivalents of thecompounds.

The present invention also comprises the new substituted benzimidazolesof Formula I, wherein R R R R and X have the significance indicatedabove excluding those cases where X is trifluoromethyl and where R ishydrogen, methyl, trifluoromethyl, or carboxy, or where R is fluoro,chloro, methyl, trifluoromethyl, methoxy or nitro, or where R and R areboth methyl or trifluoromethyl, or where R and R are the same and aremethyl or ethoxy, or where R and R are both methyl, when the remaininggroups R to R are hydrogen, or where R R R and R are all fluoro groups,and excluding those cases where X is pentafluoroethyl and either where R-R are all hydrogen or where R is fluorine and R R and R are hydrogen,or where R and R are methyl and R and R are hydrogen.

Salts of the substituted benzimidazoles embraced by the presentinvention may comprise ammonium salts, metal salts such as for examplesodium potassium, calcium, zinc, copper and magnesium salts, amine saltssuch as for example methylamine, ethylamine, dimethylamine,triethylamine, ethanolamine, triethanolamine and benzylamine salts.According to a preferred embodiment the salts are alkali metal salts.Generally the alkali metal salts are crystalline solids, readily solublein water.

The salts may be prepared by reacting the benzimidazole in aqueous oraqueous-organic solvent solution or suspension with an alkaline compoundof the metal, such as the hyroxide, or with the amine, as appropriate.The

metal salts may also be prepared by metathesis for example between thealkali metal salt of the benzimidazole and a salt of the metal. Some ofthe benzimidazoles are also basic and can form salts with strong acidssuch as hydrochloric acid.

It has been found that the substituted benzimidazoles according to theinvention generally possess physiological activity. Many of thesecompounds are useful as herbicides having post-emergent activity as wellas some pre-emergent activity, or as insecticides, or as molluscicides,or as fungicides.

The use of the active compounds in protecting keratinic material againstinsect attack, e.g., mothproofing, is the invention of the inventorsNewbold et al. and is disclosed and claimed in application Ser. No.529,248, filed Feb. 23, 1966, now US. Pat. 3,542,923.

According to one embodiment, the invention provides the followingcompounds, which are especially active as herbicides:

4,S-dichloro-2-trifluoromethyl benzimidazole,4,6-dichloro-2-trifluoromethyl benzimidazole,4,5,7-trichloro-2-trifiuoromethyl benzimidazole, 4,5,6-trichloro-2-trifiuoromethyl benzimidazole,4-nitro-5-bromo-2-trifluoromethyl benzimidazole,-chloro-6-nitr0-2-trifluoromethyl benzimidazole,4-nitro-6-chloro-2-trifluoromethyl benzimidazole,4,5,7-tribromo-2-trifluoromethyl benzimidazole,4-chloro-6-nitro-2-trifluoromethyl benzimidazole,4-nitro-2-trifluoromethyl benzimidazole, 4-chloro-2-trifiuoromethylbenzimidazole, 4,6-dibromo-2-trifluoromethyl benzimidazole,5-cyano-2-trifluoromethyl benzimidazole,4-bromo-6-chloro-2-trifluoromethyl benzimidazole,S-bromo-Z-trifluorornethyl benzimidazole,4-chloro-6-bromo-2-trifluoromethyl benzimidazole,5-iodo-2-trifluoromethyl benzimidazole,4-bromo-6-nitro-2-trifiuoromethyl benzimidazole, and4,6-nitro-2-trifluoromethyl benzimidazole.

According to another embodiment, the invention provides the followingcompounds, which are especially active as insecticides, bothagriculturally (in the treatment of plants, the soil, etc.) andindustrially (in the treatment of inanimate matter such as textiles,wood, paper, etc.).

4-chloro-2-trifluoromethyl benzimidazole, 4,7-dichloro-Z-trifiuoromethylbenzimidazole, 4-nitro-6-chloro-2-trifiuoromethyl benzimidazole,4-nitro-6-bromo-2-trifluoromethyl benzimidazole,4-bromo-5,6,7-trichloro-2-trifluoromethyl benzimidazole,4-bromo-2-trifluoromethyl benzimidazole, 4-nitro-2-trifiuoromethylbenzimidazole, 5-nitro-2-trifluorornethyl benzimidazole,4,6,7-trichloroQ-trifiuoromethyl benzimidazole,4,5,6-trichloro-2-trifiuoromethyl benzimidazole,4,5,6,7-tetrabromo-2-trifluoromethyl benzimidazole,4,6-diiodo-2-trifiuoromethyl benzimidazole,4,6,6-trichloro-5-bromo-2-trifluoromethyl benzimidazole,5-chloro-6-nitro-2-trifiuoromcthyl benzimidazole,4,6,7-trichloro-5-fluoro-2-trifiuoromethyl benzimidazole,4,5,6,7-tetrachloro-2-trifluoromethyl benzimidazole, and4,6-dibromo-5,7-dichloro-2-trifluoromethyl benzimidazole.

With the compounds of Formula I, it has been found that compounds whereat least 3 of the groups are halogen, are especially active asinsecticides and mothproofing agents. Accordingly one embodiment of theinvention is for compounds of Formula I and salts thereof, where R R R Rand X have the significance indicated herein, but where at least threeof the groups R R R and R are halogen.

According to a further embodiment, the present in- 'vention is forcompounds of Formula I and salts thereof, where R R R R and X have thesignificance indicated herein, but where at least one of the groups R RR and R is halogen and not more than two of the groups R R R and R arehydrogen. According to a yet further embodiment, the present inventionis for compounds of Formula I and salts thereof where R R R R and X havethe significance indicated herein, but where at least one of the groupsR R R and R is a cyano, amino, substituted amino, carboxyamide, thiol,sulphonic acid or a group attached to the ring through a sulphur atom,radical.

In one particular embodiment the invention provides compounds of theformula:

and salts thereof wherein R R R and R are the same or different andrepresent hydrogen or halogen with the proviso that when R or R isfiuoro, chloro or hydrogen, the remaining members of R R R and R are notall hydrogen and with the further proviso that where R or R is fluoro,the remaining members of R R R and R are not all fiuoro. Particularcompounds which may be mentioned as falling within this group ofcompounds are as follows:

5,6-dichloro-2-trifiuorobenzimidazole,4,5-dichloro-Z-trifluorobenzimidazole,

4,5 ,6-trichlor0-2-trifiuorobenzimidazole,4-bromo-5,6-dichloro-2-trifiuorobenzimidazole,4,6-diiodo-Z-trifluorobenzimidazole, S-iodo-2-trifluorobenzimidazole.

In a further particular embodiment, the invention provides compounds ofthe formula wherein R R R and R are the same or different and areselected from the group consisting of chloro, bromo and hydrogen, notmore than two of R R R and R representing hydrogen.

The invention also provides compounds according to the immediate aboveformula wherein at least one of R R R and R is chloro and not more thantwo of said groups are hydrogen.

The substituted benzimidazoles bearing an amino group are prepared bythe reduction of the corresponding nitro substituted benzimidazole.

The substituted benzimidazoles bearing nitro groups together with othersubstituents such as halogen are prepared by nitration of thecorresponding substituted benzimidazole.

The substituted benzimidazoles as indicated are prepared by reacting thecorresponding 'ortho-phenylenediamine with trifluoroacetic acid,trifluoro acetyl chloride or trifluoro acetic anhydride, or withpentafiuoropropionic acid, pentafiuoropropionyl chloride orpentafluoropropionic anhydride.

Many of the compounds according to the present invention possessfungicidal as well as insecticidal activity, and consequently theobjects treated may also be rendered antifungal.

The compounds of the invention are of particular application in thetreatment of inanimate matter for the purpose of destroying insects orrendering it resistant to insect attack. The materials so treated maycomprise for C-C F3 3a..

example wood, paper, timber, fabrics, synthetic fibers, plastics,sacking, jute, grain, flour, paint and varnish compositions, adhesives,glues, materials of constructions, etc.

The process for the'treatment of inanimate materials may comprise anymethod of contact or incorporated. Thus for example the materials may besprayed, coated or impregnated with a solution or suspension containingthe substituted benzimidazole, or if desired the material may be dippedin a bath containing said compound. Impregnation may be carried out forexample at reduced pressure or at high pressure or at high temperature,if so desired. Where appropriate the substituted benzimidazole may beincorporated into the materials to be treated. Thus for example thesubstituted benzimidazole may be incorporated into paint, varnish or dyecompositions; the resulting composition is resistant to insect attack asare articles painted or treated with them.

It is also possible to incorporate the substituted benzimidazole intosynthetic fibers or plastics during manufacture. Thus for example, inthe case of viscose, the substituted benzimidazole may be incorporatedduring manufacture by inclusion in the solution prior to coagulation andspinning. The compounds may also readily be incorporated in buildingmaterials such as plaster. 1

Many of the substituted benzimidazoles exhibit prolonged activity of theinanimate materials. The activity may persist for many months, or more,and in some cases is resistant to washing operations.

A specially preferred embodiment is the treatment of fibers, yarns andtextiles for moth proofing and related purposes. As indicated, with thesynthetic fibers, it is possible to incorporate the compounds duringmanufacture. With other fibers and textiles, the treatment according tothe invention may be carried out in any of the conventional waysincluding dipping and spraying as a separate operation or combined withother treatments such as dyeing, flameproofing, waterproofing, etc.Dipping processes may be carried out in accordance with conventionalmethods. If desired, the treatment of textiles may be combined with aconventional washing operation.

The insects and pests against which the compounds of the presentinvention provide protection include flying insects such as flies,mosquitoes, butterflies, moths, beetles, aphids, etc., crawling pestssuch as larvae, caterpillars, spiders, beetles, etc.

Many of the salts of the substituted benzimidazoles embraced by theinvention are water-soluble, and these may be used in physiologicallyactive compositions as aqueous solutions with or without wetting ordispersing agents, organic solvents, stickers and the like which arecommonly incorporated in sprays for agricultural and related purposes.However, it is generally preferred to use the salts of the substitutedbenzimidazole in association with a wetting agent.

If desired, the substituted benzimidazoles or salts thereof may bedissolved or dispersed in an organic solvent in which the substitutedbenzimidazole may be soluble or insoluble. Such solvents include naturalvegetable oil, such as olive oil or arachis oil, or petroleum oils.

The substituted benzimidazoles or salts thereof may also be admixed witha wetting agent with or without an inert diluent to form a wettablepowder which is soluble or dispersable in water, or may be mixed withthe inert diluent to form a solid or powdery product.

Inert diluents with which the substituted benzimidazoles and saltsthereof may be incorporated include solid inert media comprisingpowdered or divided solid materials, for example, clays, sands, talc,mica, fertilizers and the like, such products either comprising dust orlarge particle size materials.

The wetting agents used may comprise anionic compounds such as forexample, soaps, fatty sulphate esters such as dodecyl sodium sulphate,fatty aromatic sulphonates such as alkyl-benzene sulphonates or butylnaphthalene sulphonate, more complex fatty sulphonates such as the amidecondensation product of oleic acid and N- methyl taurine or the sodiumsulphonate of dioctyl succinate.

The wetting agents may also comprise non-ionic wetting agents such asfor example condensation products of fatty acids, fatty alcohols orfatty substituted phenols with ethylene oxide, or fatty esters andothers of sugars or polyhydric alcohols, or the products obtained fromthe latter by condensation with ethylene oxide, or the products known asblock copolymers of ethylene oxideand propylene oxide. The wettingagents may also comprise cationic agents such as for example cetyltrimethylammonium bromide and the like.

For molluscicidal use the benzimidazole may for example be made into agranule or pellet, for example of plaster of Paris, which may bescattered in an aquatic habitat of the molluscs, and from which thebenzimidazole may be leached, or dissolved into a spreading oil such asdiesel or lubricating oil with a wetting agent such as oleic acid, whichmay be applied to the Water surface. The compounds of the presentinvention also provide a process for the purification of water bytreatment in this Way. Edible substances attractive to molluscs withwhich the benzimidazoles may be admixed include fungi, oilcake, fruitwaste, lucerne flour, cereals, cereal products, vegetables, vegetableproducts, bran, biscuits and the like.

The physiologically active compositions may contain in addition to thesubstituted benzimidazole or salts thereof, other physiologically activematerials such as herbicides, insecticides, fungicides andmolluscicides.

The following examples are given to illustrate the present invention;the parts and percentages are by weight unless otherwise indicated.

EXAMPLE 1 50 parts of 3,4,5,6-tetrachloro-o-phenylenediamine and 62parts of trifluoroacetic acid were heated for 16 hours at C. withprotection from the ingress of moisture. The excess trifiuoroacetic acidand the water formed in the reaction were then removed under reducedpressure and the final traces removed by keeping over solid sodiumhydroxide under high vacuum. The residual solid cake was powdered andheated with 3500 parts of boiling benzene. The boiling solution wasfiltered from a small amount of insoluble material treated with charcoaland set aside to crystallize. The product 4,5,6,7-tetrachloro-2-trifiuoromethylbenzimidazole (33.3 parts; 50% yield) separated as fineneedles, melting point 285 C., unchanged by further recrystallization.

Analysis.-Found (percent): C, 30.90; H, 0.30; Cl, 43.0; F, 17.10; N,8.55. C HCl F N requires (percent): C, 29.66; H, 0.31; Cl, 43.78; F,17.60; N, 8.65.

EXAMPLES 23 'In an analogous way to Example 1 the following compoundswere prepared:

4,5,6-trichloro-2-trifiuoromethylbenzimidazole (melting point 226228 c.

4,5,7-trichloro-2-trifluoromethylbenzimidazole (melting point 240-242c.)

4-bromo-5,6-dichloro-2-trifluoromethylbenzimidazole (melting point235236 C.).

EXAMPLE 4 7 off-white solid (17 parts 62% yield), melting point 213-4"C.

Analysis.--Found (percent): C, 37.95; H, 1.25; N, 11.05; Cl, 27.55. C HClgF N requires (percent): C, 37.67; H, 1.19; N, 10.98; Cl, 27.81.

EXAMPLES 5-1 6 In an analogous manner to Example 4 the followingcompounds were prepared:

4,6-dichloro-2-trifluoromethylbenzimidazole (melting point 175-7" C.)4,7-dichloro-Z-trifluoromethylbenzimidazole (melting point 273-4 C.)4-nitro-6-chlor0-2-trifluoromethylbenzimidazole (melting point 148-150C.) 4-chloro-6-nitro-2-trifluoromethylbenzimidazole (melting point 206-8C.) 5,6-dichloro-2-trifiuoromethylbenzimidazole (melting point 244-5 C.)4-bromo-5,6,7-trichloro-2-trifluoromethylbenzimidazole (melting point260-272 C.) 4-chloro-2-trifluoromethylbenzimidazole (melting point159-161 C.) 5,6-dimethoxy--trifluoromethylbenzimidazole hydrochloride(melting point 211212 C.) 5,6-dinitro-2-trifiuoromethylbenzimidazole(melting point 242243 C.) 4,7-dibromo-2-trifiuoromethylbenzimidazole(melting point 267-270 C.) 5-cyano-2-trifluoromethylbenzimidazole(melting point 192 C.)4,6,7-trichloro-5-methyl-2-trifluoromethylbenzimidazole (sublimes above145 C.)

EXAMPLES 17-20 16.4 parts of pentafiuoropropionic acid were added to10.5 parts of 3,4,S-trichloro-o-phenylene diamine and the 4,6,7trichloro-S-methyl-2-pentafluoroethylbenzimidazole (melting point 2605C.)

EXAMPLE 21 A herbicidal composition was prepared by grinding together100 parts of 5-nitro-2-trifluoromethylbenzimidazole, 200 parts of chalkand parts of sorbitan monooleate, forming a wettable powder. Thewettable powder was dispersed in water for spraying purposes and wasused as a post-emergent selective herbicide at a rate of 355 grams perhectare.

EXAMPLE 22 A herbicidal composition was made by preparing an aqueousconcentrate of the sodium salt of5-chloro-2-trifiuoromethylbenzimidazole and Lissapel NX. This aqueousconcentrate could be diluted with further water for spraying.

EXAMPLE 23 Peas, mustard, linseed, buckwheat, sugarbeet, barley, mayweedand chickweed were grown in John Innes No. 1 potting compost in aluminumpans (17.75 x 9.25 x 5 cm.) two species to a pan. When the plants hadbetween 2 and 5 true leaves they were sprayed with an aqueous solutionof the sodium salt of benzimidazole indicated in the following table atrates equivalent to 11.36, 5.68, 2.84, 1.42, 0.71, 0.35 and 0.18 kg. perhectare in 180 litres.

After seven days in a controlled environment room at 22 C. with 14hours/ day illumination of 300 meter candles and at 7 5-90% relativehumidity, the plants were assessed for any herbicidal effect.

The herbicidal effect of the compounds was assessed as an average forthe eight species, on a scale where 100 indicates complete kill and 0indicates no herbicidal activity. The results are given in the followingtable.

Average toxicity Rates in kgJheetare 11.36 5 .68 2.84 1.42 0.7 10 .35 018 Compound:

4,5-diehloro-2-trifluoromethylbenzimidazole 84 81 79 72 57 534,6-dichloro-2-triflu0romethylbeuzimidazole- 98 97 96 93 88 74 574-nitro-6-chloro2-trifluorornethylbenzimidazole 96 96 96 95 89 76 724-ch1oro-G-nitro-Z-trifiuoromethylbenzimidazole 94 93 93 86 84 814,5,6,7-tetraehl0ro-2-t1ifluoromethylbenzimidazole- 72 71 66 62 534,5,fi-triehloro-2-trifluoromethylbenzimidazole- 100 96 96 94 89 84 614,5,7-trichloro-2-trifluoromethylbenzimidazole 89 84 75 73 71 67 705-chloro-2-triflu0romethylbenzimidazole 86 78 76 65 584-chloro-2-trifluoromethylben dimidazole 93 87 72 67 662,5-bi(trifiuoromethyl)benzimidazole 95 88 80 79 74 495-nitro-2-trifluorornethylbenzemidazole 95 73 66 62 60 574,5,6-trich10r0-2-pentafluoroethylbenzimidazole 94 94 93 91 90 78 515-nitro-2-pentafiuoroethylbenzirnidazole 96 93 91 mixture heated for 15hours on a steam bath. The 80110. EXAMPLE 24 cake formed was stirredwith 10% aqueous sodium hydroxide solution, and the insoluble runreacteddiamine filtered off. The alkaline liquor was made almost neutral by theaddition of concentration hydrochloric acid and then made just acid bythe addition of glacial acetic acid. The brown oil obtained wasextracted into benzene and the liquor clarified with charcoal. Thebenzene liquor was extracted with 0.880 ammonia and the alkaline extractneutralized with concentrated hydrochloric acid and made just acid withglacial acetic acid.

The precipitated product was filtered off and recrystallized fromtoluene to give 4,5,6-trichloro-2-pentafluoroethylbenzimidazole in ayield of 4 parts (25%), melting point 2067.5 C.

Analysis-Found (percent): N, 8.75; CI, 32.40. C I-I Cl F N requires(percent): N, 8.50; Cl, 32.28.

The following compounds were prepared in an analogous way:

5-nitro 2 pentafluoroethylbenzimidazole (melting point Peas, mustard,linseed, barley, maize and ryegrass seed sown in John Innes No. 1potting compost in which 5-nitro-2-trifluoromethylbenzimid azole hadbeen incorporated at rates equivalent to 24 and 12 parts per millionweight/volume of soil or equivalent to a surface application of 11.36and 5.68 kilograms per hectane. The plants were grown in aluminum pans(17.75 cm. x 9.25 cm. x 5 cm.) one species to a pan.

After 21 days growth in a controlled environment room the plants wereassessed for any herbicidal effects when it was found that thegermination of mustard and linseed had been suppressed by both rates,the germination of ryegrass had been severely suppressed and thesurviving plants were markedly stunted and incapable of normal growth,whilst peas, barley and maize were relatively unaffected.

EXAMPLE 25 Solutions containing 10, 3, 1, 0, 3 and 0.1 parts per million(weight by volume) of the compounds listed below were made in aerateddistilled water. 100 milliliters aliquots of the solution were placed inscrew cap glass jars, 4.5 centimeters diameter by 8.5 centimeters high,which just filled them to the brim. Five young specimens g-ehloro-igrii2 fifi-trichlotiig-l uororne y ll 110101118 y of the bilharala vectorsnail, Australorbzs glabratus, were benzimidazole benzimidazole thenplaced 1n each vessel and a perforated 11d screwed on to prevent themleaving the water. After a 24 hour 50% 95% 50% 95% exposure period thesnails were removed from the soluirtytophthomlpalmivora g3 8 fig 5gCTN/(17211 80 (I'll/Z tlons of the compounds and placed in aerateddistilled Bough-mm, 10 10 10 water for a further 48 hours recoveryperiod, before an l lgp z 33 g g3 g3 CT 161 mm a 0 a mm assessment ofmortality was made. I Fame, ("mom 10 10 10 10 The results obtained aresummanzed 1n the following 10 table each value being the average ofthree replications.

Percent mortality after 72 hours at Compound 10 p.p.rn. 3 p.p.m. 1p.p.m. 0.3 p.p.m. 0.1 ppm.

1 4-bromo-5 6,7-trichl0r0-2-trifluoromethylbenzimidazole 100 100 100 10050 2. 4,6,7-trichloro-5-methyI-Z-trifluoromethylhenzimidazole 100 100 6050 0 3- 4,5-dichloro-Z-trifluoromethylbenzimidazole 100 100 100 0 0 44-nitro-6-chloro-2-trifluorornethylbeuzimidezole. 100 100 100 O 0 5--4,5,6-trichloro2-trifluoromethylbenzimidazole 100 100 100 3 0 64,6,'I-triohloro-2-trifiuoromethylbenzimidazole 100 100 6 0 0 74,5,6,7-tetrachloro-2-trifluoromethylbenzimidazole 100 100 80 0 0EXAMPLE 31 These results indicate that each compound possesses a markedmolluscicidal activity.

EXAMPLE 26 An insecticidal composition was prepared by grinding together100 parts of 4.7-dichloro-2z-trifluoromethylbenz imidazole, 200 parts ofchalk and 50 parts of sorbitan mono-oleate forming a wettable powder.This wettable powder was dispersed in water and sprayed or painted ontowalls giving a long residual insecticidal eflect.

EXAMPLE 27 A molluscicidal composition was prepared by admixing 100parts of diesel oil, 5 parts of 4-bromo-5,6,7-trichloro-2-trifluoromethylbenzimidazole and 2 parts of oleic acid so as to forman oil solution. This oil was sprayed onto water surfaces and spreadover the water allowing the active ingredient to dissolve therein.

EXAMPLE 28 9 centimeters diameter filter paper in 9 centimeterscrystallizing dishes were treated with 1 millimeter portions of acetonesolutions of 4,7-dichloro-2-trifluoromethylbenzimidazole atconcentrations giving deposits equivalent to 1087, 108.7, 10.87 and 5.44mg. /square meter. Batches of female house flies (Musca domestica)lightly anaesthetized with carbon dioxide, were introduced into thedishes after the solvent had evaporated, and a glass lid was placed overeach dish. After 24 hours the dishes were examined and it 'was foundthat there was a complete kill of flies at all four concentrations.Flies maintained under similar conditions in the absence of the chemicalwere unaffected.

EXAMPLE 29 11 grams of 3-amino-5-mercapto-ortho-phenylenediaminedihydrochloride were refluxed for eight hours with 12 milliliters oftrifluoroacetic acid. The solid product comprising2-trifluoromethyl-4-trifluoroacetamido-6-mercapto benzimidazole wasfiltered oif, washed with a little trifluoroacetic acid andrecrystallized from benzene giving 4 grams of the crystalline product ofmelting point 229-231" C.

EXAMPLE 30 Nutrient medium known as potato-dextrose agar medium was madeup in molten condition with incorporation of compounds of the inventionat various concentration levels. The medium was then allowed to set inpetri dishes and plugs of actively growing mycelium of the fungi listedbelow were placed on the plates. The concentrations which were found torestrict growth to (a) 50%, (b) 95% that observed in control plates arerecorded.

The compound 4,5,7-trichloro-Z-trifluoromethyl benzimidazole was groundin presence of equal weight of china clay and 10% of sorbitan monooleate to give a wettable powder and this was suspended in water to givevarious concentrations of active ingredients and then sprayed to run-offon cucumber leaves which were subsequently dusted with spores of themildew Erysiphe cichoracearum. Development of the fungus in comparisonwith that on untreated leaves is recorded.

Concentrations, p.p.m.: Percent developed EXAMPLE 32 30 parts of2,5-di-(trifluoromethyl)benzimidazole, 30 parts of industrial ethylalcohol, 4.8 parts of sodium hydroxide and 80 parts of water were foundto form a clear aqueous solution which on cooling deposited crystals ofthe sodium salt.

Analysis.--Found (percent): F, 41.10; Na, 8.45. C H F N Na (percent): F,41.29; Na, 8.33.

EXAMPLE 34 29 parts of 4,5,7-trichloro-Z-trifluoromethyl benzimidazolewere dissolved with agitation in parts of a 10% solution oftrimethylamine in water giving an aqueous solution of the trimethylaminesalt of 4,5,7-trichloro-2- trifiuoromethyl benzimidazole.

EXAMPLE 35 22 parts of 5-chloro-2-trifiuoromethyl benzimidazole, 6 partsof potassium hydroxide, 30 parts of methyl alcohol, and 70 parts ofwater were heated together giving a clear solution which on partialevaporation and cooling deposited crystals of the potassium salt of5-chloro-2-trifluoromethyl benzimidazole.

11 12 Analysis.Found (percent): C, 37.21; H, 1.19; N,4-chloro-6-bromo-2-trifiuoromethylbenzimidazole 10.86; Cl, 13.93. K,14.77. C H ClF N K requires (per- (M.P. 194 C.) cent): C, 37.15; H,1.17; N, 10.83; Cl, 13.89; K, 15.09.5-iodo-2-trifiuoromethylbenzimidazole (M.P. 222-224 C.)

EXAMPLE 36 5 4-bromo-6-nitro-2-trifluoromethylbenzirnidazole 23.1 gramsof 5-nitro-2-trifiuoromethylbenzimidazole were dissolved in 250milliliters of absolute alcohol, 4GdmItIO'Z'mfiUEromethylbenzlmldazoleAdams platinum catalyst was added and hydrogen passed 159-160 throughuntil 3 mols of hydrogen had been absorbed4nitro'6'bromo'zgtrifiuoromethylbenzimidazole v and the solution whichwas initially red-brown turned 0 165467 green. The alcohol was removedby vacuum distillation at 4'bromo'2trlfluoaomethylbenzlmldazole 80 C. togive a black oily residue, which was dissolved 151-153 in 40 millilitersof anhydrous ether and dry hydrogen4,567tetmbrom8Z'mfiuoromethylbenzlmldazole chloride gas was passedthrough until precipitation was Q) complete. The solid was filtered off,washed with ether, 476d11d0-2"?lfluoromethylbenzumdazole dried andrecrystallized from concentrated hydrochloric 195 acid to give grams of5 amino z tl.ifiuoromethylbenz4,6,7-trlchlorg-5-bromo-2-trlfluoromethylbenzlmldazole imidazoledihydrochloride. (Melting point 262 C. with (MR 276 decomposition) 5-chloro-6-nitro-2-trifluoromethylbenzimidazole A l d t 34.8 H, 3.05; CI,20 s 2: 22132 2 iaquireso (percent). C,4,6,7-trichloro-5-fiuoro-2-trifluoromethylbenzimldazole (M.P. 246-248C.) 1533' 4,6-dibromo-5,7-dichloro-2-trifluoromethylbenzimidazoleEXAMPLE 37 (M.P.) 252 C.). To a mixture of 15.5 grams of4,5,6-trichloro-2-tri- 25 EXAMPLES 57 5 fluoromethylbenzimidazole and 9millilitres of concentrated sulphuric acid were added 18 milliliters offuming An acetone solution of the compound was p y nitric acid in 1millilitre portions. When the initial reac- Onto 7 diameter discs ofCabbage leaf at Such a $011- tion had subsided the mixture was refluxedon an oil centfation and Volume as to Produce deposits of 13 bath forone hour. The mixture was cooled and poured onand mlcl'ogfams/sq- Afterthe Solvfint had P to ice, the precipitate filtered off, washed withwater, dried rated the discs were Placed in 9 diametel' Petri dishes andrecrystallized from benzene giving 12.8 grams f and infested with tensecond instar larvae of the cabbage 4,5,6-tri hloro-7-nitro 2 trifluo thlben i id l white butterfly-Pieris brassicae. The mortalities ob-(rnelting point 221-223" C.). tained after 48 hours exposure aresummarized in the Analysis.-Found (percent): C, 28.80; H, 0.30; CI,following table.

Percent mortality at- Compound 65 1 13 1 6 .5 1

57 4-bromo-2-trifluorometh3 lbenzimidazole 100 90 60 584,5,6,7-tetra-bromo-Z-trifluoromethylbenzimidazole 100 100 100 594,6-di-iodo-2-trifluoromethylbenzimidazole 100 0 1 Micrograms per squarecentimeter.

31.35; N, 12.55. C HCl F N O requires (percent): C, 4.5 EXAMPLES 6061 2873' H 0.30 Cl 31.79 N 12.56.

Acetone concentrates of the compounds were diluted ffi z g i g f fjgfglgh g gz fififgg in water to give solutions containing 1000, 300 and100 e g P p p parts per million (p.p.m.) of active ingredient. 2 cm. di-

EXAMPLES 38456 50 ameter discs of french bean leaf (Phaseolus vulgaris)were sprayed with the solution which were then placed in moist filterpapers and immediately infested with 20 adult red spidermites-Tetranychus telarius. The discs In analogous manner to Example 4,the following compounds were prepared:

4-nitro-5-bromo-2-trifiuoromethylbenzimidazole were examined after 48hours when the mortality was (M.P. 1l9-121 C.) recorded. The results aresummarized in the table below.

Percent mortality at- 1, 000 300 100 Compound p.p.m. p.p.m. p.p.m.

60.--" 4,6-di-iodo-2 trifluoromethylbenzimidazole 100 100 100 61"...fi-bromo-4-nitro-2-trifluorornethylbenzimidazole 100 100 1005-chloro-6-nitro-2-trifiuoromethylbenzimidazole EXAMPLES 62 63 (M.P.197-198 C.) 65

4,5 ,7-tribromo-2-trifluoromethylbenzimidazole (M.P. 216-218 C.)4-nitro-2-trifluoromethylbenzimidazole Acetone concentrates of thecompounds were added to whole-meal flour to produce concentrations of300 and (MR C) 100 p.p.m. wt. of compound per wt. of flour. The treated4,6-dibromo-2-trifluoromethylbenzimidazole flour was placed in smallglass specimen tubes (3" x 1") 181482, C") and 10 adult flour beetlesTribolium confusumadded to 2fi gg1 each. After 10 days incubation at 25C. and 60% relas bmr'no 2 trifiu0romethy1benzimidazole tive humidity themortality of the beetles was assessed.

(M.P. 139.5-141" C.) The results given in the following table.

Percent mortality 300 100 Compound p.p.m. p.p.m.

62 4,6-di-iodo-2-trifluorornethylbenzimidazole 100 40 634,5,6.7-tetra-bromo-2-trifluoromethylbenzimidazole 100 100 EXAMPLE 64onto 2 cm. discs of French bean leaves mounted on wet 9 cm. filterpapers were treated with an acetone solution of 4bromo-2-trifluoromethylbenzimidazole such as to produce depositsequivalent to 300, 100 and 30 milli grams per square foot. When thesolvent had evaporated the filter papers were placed in crystallizingdishes (9 x 4 cms.) together with about 50 adult female houseflies, Musca domestica. After 24 hours exposure the treatments were examinedwhen it was found that all rates had given complete kill of the insects.

EXAMPLES 65-68 Peas (Psuma sativum), mustard (Sinapis alba), linseed(Lz'num 'usitatissimum), beet (Beta vulgaris), buckwheat (Fagopyrumesculentum), and barley (Hordeum vulgare var. Prct0r) were grown insmall aluminum pans (7%" x 3%" x 2"), containing John Innes No. 1potting compost-two species to a pan. When the plants were about 2-3"high and the first true leaves had fully expanded they were sprayed withacetone/water solutions or suspensions of the compounds indicated belowat rates equivalent to 10 and 1% lbs. active ingredient in 80gallons/acre. After 7 days growth in a controlled environment room (22C.; 14 hours artificial illumination per day at 1200 ft. candles) theactivity of the compounds against each species was assessed according toa herbicidal index where 0=no elfect and 100=complete kill. The resultsare summarized in the following table.

filter paper and the discs were then covered with adults of greenhousered spider mite (Tetranychus telarius). With every compound a completekill of the mites are obtained within 24 hours at both concentrations.

(72) S-nitro-2-trifiuoromethylbenzimidazole, (73)4,5,6-trichloro-2-trifluoromethylbenzimidazole, (74)6-chloro-4-nitro-Z-trifluoromethylbenzimidazole.

EXAMPLES 75-85 An acetone solution of each of the substitutedbenzimidazole indicated below was sprayed onto 7 cm. discs of cabbageleaves so as to give coatings of 3 micrograms of active ingredient persquare centimeter. After the solvent had evaporated the discs wereplaced in 9 cm. petri dishes and each infested with ten second instarlarvae of the cabbage-white butterfly (Pieris brassicae). With everycompound a complete kill of the larvae was obtained within 24 hours.

(75) -4-chloro-2-trifiuoromethyl benzimidazole,

(76) S-cyano-2-trifiuoromethylbenzimidazole,

(77) 5,6-dichloro-2-trifiuoromethylbenzimidazole, (78)4,7-dichloro-2-trifluoromethylbenzimidazole, (79)4,7-dibromo-2-trifluoromethylbenzimidazole,

'( 80) 6-chloro-4-nitro-2-trifluoromethylbenzimidazole, (815-chloro-6-nitro-2-trifiuoromethylbenzimidazo1e,

Herbicidal activity Rate 1b. Mus- Lin- Buck- Sugar- Average Compoundacre Peas tard seed wheat beet Barley toxicity 655-bromo-4nitro-Z-trifiuoromethylbenzimidazole. 10 85 100 100 100 100 3587 1% 75 98 90 15 100 10 65 66 5-cyan0-2-trifluoromethylbenzimldazole 10100 100 100 100 8 76 1% 5 99 95 100 100 0 67 67S-bromo-Z-trifiuoromethylbenzimidazole 10 90 100 100 100 100 75 94 1% 2595 100 100 100 25 74 68 4-bromo-5-nitro-2-trlfiuoromethylbenzimldazole.10 100 100 100 100 60 85 1% 18 85 98 100 100 20 70 EXAMPLES 69-71 Seesof peas (P. sativum), mustard (S. alba), linseed 50 (L. usitatissimum),maize (Zea mays), barley (H. vulgare), and ryegrass (Lolium sp.) weresown in small aluminum pans containing John Innes No. 1 potting compostinto which had previously been mixed the compounds indicated below at arate of 24 p.p.m. (wt. of active ingredient per vol. of soil equivalentto an application of 10 lbs./acre mixed to depth of soil in pans). After22 days growth in a controlled environment room (22 C.; 14 hours lightper day) the plants were examined for sign of herbicidal activity.Damage was assessed on an index where 0=no effect and 10=cornplete kill.The results are summarized in the following table:

(82) 4,5,6-trichloro-2-trifluoromethylbenzimidazole,

(83) 4,6,7-trichloro-2-trifluoromethylbenzimidazole,

(84) 5-fluoro-4,6,7-trichloro-2-trifiuoromethylbenzimidazole,

(85) 5-brorno-4,6,7-trichloro-Z-trifluoromethylbenzimidazole.

EXAMPLES 86-90 9 centimeter diameter filter papers were treated withacetone solutions of the substituted benzimidazole indicated below andwhen the solvent had evaporated, were placed in crystallizing dishes (9cm. x 4 cm.). The con- Herbicldal index Rate 1b. Mus- Lin- Rye- AverageCompound acre Peas tard seed Maize Barley grass toxicity 695-cyano-2-trifluoromethylbenzimidazole 10 85 100 100 45 35 80 745-bromo-2-trifluoromethylbenzimidazole 10 24 100 100 0 13 49 48 714-bromo-6-nitro-2-trifiuoromethylbenzimidazole. 10 0 100 100 60 71EXAMPLES 72-74 An acetone concentrate of each of the substitutedbenzimidazole indicated below was diluted in water to give solutionscontaining 30 and parts per million (p.p.m.) of active ingredient. Thesesolutions were sprayed centrations of the solutions were adjusted sothat 1 millilitre aliquots deposited on the papers produced depositsequivalent to 300, 100 and 30 mg./sq. foot.

Adult female houseflies (Musca domestica), lightly anaesthetized withcarbon dioxide were then introduced into the dishes and a glass lidplaced over each. When examined after 24 hours, all treatments werefound to have given a complete kill of the insects.

(86) 4-chloro-2-trifluoromethylbenzimidazole, (87)4-nitro-2-trifluorornethylbenzimidazole,

( 88 4,7-dichloro-2-trifluoromethylbenzimidazole,

( 89 6-chloro-4-nitro-2-trifluoromethylbenzimidazole, (90)6-bromo-4-nitro-2-trifluoromethylbenzimidazole.

EXAMPLES 91-93 Acetone solutions of the benzimidazole indicated belowwere added to flour at rates giving 300, 100 and 30 ppm. weight ofactive ingredient per weight of flour. After the solvent had evaporated,the flour at each level of concentration was thoroughly mixed. Portionsof the treated flour were placed in glass tubes -(7.5 cm. x 2.5 cm.) andten adult flour beetles (Tribolium confusum) added to each tube. Afterdays all treatments with all the compounds were found to have given acomplete kill of the beetles.

(91) 4,6,7-trichloro-Z-trifiuoromethylbenzirnidazole,

(92) S-fluoro-4,6,7-trichloro-2-trifluoromethylbenzimidazole,

(93) 5-bromo-4,6,7-trichloro-2-trifluorornethy1- benzimidazole.

EXAMPLES 94-99 The substituted benzimidazoles indicated below wereformulated into wettable powders of the following composition.

Percent Substituted benzimidazole 25 Dispersing agent (Dyapol PT) 5Wetting agent (Hoe 82/268) 1 China clay 62 The compositions weresuspended in water and sprayed onto copy paper so as to give deposits ofthe substituted benzimidazole of 30 mg., mg. and 3 mg. per square foot.

Adult female mosquitoes (Aedes aegypti) were transferred to cages usingthis copy paper as the floor and were then removed to normal storagecages after 1, 2 and 4 hours exposure. Mortalities were assessed 24hours, and are given in the following table, expressed as per-Persistence Compound: i time, days4,7-dichloro-Z-trifluoromethylbenzimidazole 43 6-chloro-4 nitro 2trifluoromethylbenzimidazole 56 4-chloro-2-trifiuoromethy1benzimidazole26 4-nitro-2-trifiuoromethylbenzimidazole 206-bromo-2-trifiuoromethylbenzimidazole 20 6-bromo-4-nitro 2trifluoromethylbenzimidazole Over 57 EXAMPLES '106107 Absorbent cottonwool pads (approximately 9 centimeters diameter by 1 centimeterthickness) were placed in petri dishes (9 centimeter diameter) andsoaked with 10 millilitres of a solution containing 0.1% of the sodiumsalt of the substituted benzimidazole indicated below and 5% of glucose.Other pads were prepared using glucose and water only. The pads wereplaced in cages (12 x 12 x 12 inches) containing a mixed population ofabout 100 flies. The cages contained either one treated and oneuntreated pad or two untreated pads. When the cages were examined after16 hours all the flies in those containing a treated pad were found tohave been killed, as compared with no kill in the control cages. Thepads were then removed and after moistening with distilled water toreplace evaporation losses placed in a second series of cages. Againafter 16 hours all flies in those containing the treated pads were foundto have been killed. The experiment was continued for one month duringwhich time the treated pads always gave a complete kill during theexposure period.

In a separate experiment, 2. treated pad only was placed in a cagecontaining a mixed population of flies, the cage being provided with anoperating armhole. The flies were kept under observation and as soon asone had been seen to probe the pad with its proboscis for 30 seconds itwas transferred to a separate storage cage. The flies were all found tobe dead when observed four hours after transfer.

(106) 4,7-dichloro-2-trifiuoromethylbenzimidazole. (107)4-nitro-6-chloro-Z-trifinoromethylbenzimidazole.

EXAMPLE 108 cent kill. A suspension containing 1 part of6-bromo-4-n1tro-2- Mortalities alt- 30mg. 10 mg. 3mg. Exposure per perper Compound time, hrs. sq. ft. sq. ft. sq. ft.

4,7-dichloro-2-trifluoromethylbenzimidazole. a 3

6-chloro+nitro-2-trifluoromethylbenzimidazole.. 1

4-chloro-2-trifluoromethylbenzimidazole4-nltro-2-trlfluoromethylbenzimidazole z.-.

6hromo-2-trifluoromethylbenzlmidazole 16-bromo4'nitro-2-trifluoromethylbenzimidazole. 1

EXAMPLES l00105 Filter papers were treated with aqueous sugar solutionscontaining the sodium salt of the substituted benzimidazole indicatedbelow, so as to give a deposit of the active ingredient of 100 mg./ sq.foot.

Adult houseflies (Musca domestica) were transferred to cages containingthis filler paper on the floor, and left for 24 hours, and mortalityobserved. In each case 100% mortality was obtained. The papers werestored in the open and at intervals the papers were tested again, todetermine the number of days storage required for the mortality to fallto This persistence time in days is given in the following table.

trifluoromethylbenzimidazole in 1000 parts of water was prepared bydiluting a 20% solution in acetone with a 0.05% solution of octylcreosol polyethylene oxide condensate in water. This was further dilutedto give suspension containing 600, 300 and p.p.m. of active compound andthese were sprayed at a rate equivalent to 50 gals/acre on young fieldbeans (Vicia faba) infested with adult apterous vetch aphids (Megouraviciae). After treatment the plants were enclosed in glass cages withgauze tops for ventilation. All treatments produced complete kill of theaphids in 24 hours as compared with no kill on control plants.

1 7 EXAMPLES 109-117 0.1 gram of each of the substituted benzimidazoleindicated below were dissolved in 20 milliliters of ethylene glycolmonomethyl ether. This solution was stirred at room temperature with 400milliliters of water. 10 grams of previously Well wetted wool flannelwere introduced into this liquor and, with good agitation, the liquorwas heated to 90 C. for 15 minutes. Then 80% formic acid in amountcomprising 2% of the flannel was added, and the flannel agitated in theliquor for another 30 minutes at the same temperature. The bath was thencooled and the treated wool flannel well rinsed under running tap water,centrifuged and dried.

The dried flannel was then tested as to fastness against Tineollabisseliella (moth) caterpillars and larvae of Attagenus piceus andAnthrenus vorax by the methods set out in the Swiss Association forStandardization leaflets No. 95,901 and 95,902. This was done byexposing 4 pieces cut for example, from the material of the same size toattack by the caterpillars or larvae for 14 days under constanttemperature and humidity conditions (28 C./65% humidity). Fifteencaterpillars or larvae were placed on each piece of material. The factsdetermined by the test were as follows:

(a) The number surviving out of thirty caterpillars or larvae.

(b) The average relative loss in weight of the pieces of materialcalculated on an untreated sample of the same size under the sameconditions.

With every compound, there was a complete kill of the caterpillars orlarvae, and the loss in weight of the fibre was in the range 5%. Withthe control samples, all thirty caterpillars or larvae were alive, andthe loss in weight of the fibre was in the range 50100%.

'( 109) 2,S-bis-trifluoromethylbenzimidazole,

( 1 10) 2-trifluoromethyl-4-nitro-6-chlorobenzimidazole,

( 1 11 Z-trifluoromethyl-4,7-dichloro-benzimidazole,

( 1 12) 2-triflu0romethyl-4,5,6-trichloro-benzimidazole,

( 113 2-trifluoromethyl-4,5,7-trichloro-benzimidazole,

( 1 14) 2-trifluoromethyl-4, ,6,7 -tetrachloro-b enzimidazole,

(1 15 2-trifluoromethyl-4,7-dibromo-benzimidazole,

( 1 16) Z-trifluoromethyl-4,7-dibromo-5-chloro-benzimidazole,

( 1 17) 2,5 -bis-trifiuoromethyl-6-chloro-benzimidazole.

EXAMPLES 1 18-127 Two parts of each of the substituted benzimidazolesindicated below were incorporated into 98 parts of a usual commerciallight duty detergent for textiles which comprises, for example, 20 to30% sodium dodecylbenzene sulphonate or sodium lauryl alcohol sulphate,5 to sodium tripolyphosphate or sodium ethylenediamine tetraacetate, and60 to 75 parts of sodium sulphate. A washing liquor was prepared whichcontained 2.5% of the light duty detergent mixed with the substitutedbenzimidazole and wool flannel was washed therein at 34-40 C. (liquor towool ratio 20:1). The washed wool sample was then rinsed with coldwater, centrifuged and dried.

The dried sample was then tested as to fastness against Tineollabissliella (moth) caterpillars and larvae of Attagenus piceus andAnthrenus vorax by the methods set out in the Swiss Association forStandardization leaflets No. 95,901 and 95,902. This was done byexposing 4 pieces cut from the material of the same size to attack bythe caterpillars or larvae for 14 days under constant temperature andhumidity conditions (28 C./ 65 humidity). Fifteen caterpillars forlarvae were placed on each piece of material.

The facts determined by the test were as follows:

(a) The number surviving out of thirty caterpillars or larvae.

(b) The average relative loss in weight of the pieces of materialcalculated on an untreated sample of the same size under the sameconditions.

With every compound, there was a complete kill of the caterpillars orlarvae and the loss in weight of the fibre was 0-5%. With the controlsamples, all thirty caterpillars or larvae were alive and the loss inweight of the fibre was in the range 50-100%.

Similar results were also obtained where the wool was dry cleaned withdry cleaning solvents which contain corresponding amounts of thesubstituted benzimidazole indicated below.

( 1 18 2-trifluoromethyl-4,5,6-trichloro-7-bromobenzimidazole,

( 1 19) 2-trifiuor omethyl-4,7-dichloro-benzimidazole,

( 2-trifluoromethyl-4,5,6-trichloro-benzimidazo1e,

( 121 2-trifluoromethyl-4,5,7-trichloro-benzimidazole,

( 122) 2-trifluoromethyl-4,7-dibromo-benzimidazole,

(123) 2,5-bis-trifluoromethylbenzimidazole,

(124) 2-trifluoromethyl-4-nitro-6-chl0robenzimidazole,

(125 2-trifluoromethyl-4,5,6,7-tetrachloro-benzimidazole,

( 126) 2-trifluoromethyl-4,7-dibromo-5-chloro-benzimidazole,

(127) 2,S-bis-trifluoromethyl-6-chloro-benzimidazole.

What is claimed is: 1. A compound of the formula N g \C-C F3 3- wheerinR R R and R are the same or different and are selected from the groupconsisting of chloro, bromo and hydrogen, not more than two of R R R andR representing hydrogen and at least one of said groups being chloro.

2. 5,6-dichloro-2-trifluoromethylbenzimidazole. 3.4,5-dichloro-Z-trifluoromethylbenzimidazole. 4.4,5,6-trichloro-2-trifluoromethylbenzimidazole. 5.4,6-diiodo-2-trifluoromethylbenzimidazole.

References Cited UNITED STATES PATENTS 3,528,798 9/1970 Pfeilfer260-3092 FOREIGN PATENTS 6410413 3/ 1965 Netherlands 260-3092 1,170,73711/1969 Great Britain 260-3092 1,430,139 l/1966 France 260-3092 659,3848/1965 Belgium 260-3092 1,144,620 3/ 1969 Great Britain 260-3092 OTHERREFERENCES Morgan: J. Chem. Soc. (London), 1961, pp. 2344-5 relied on.

Brooke et al.: J. Chem. Soc. (London), 1961, pp. 802-7.

Fara et al.: Bollettino Dell Instituto Sieroterapico Milanese, vol. 42,No. 11-12, pp. 630-37 (1963).

Conant et al.: The Chemistry of Organic Compounds, 3rd ed. pp. 24-5, NewYork, Macmillan, 1947.

Latimer et al.: Reference Book of Inorganic Chemistry, p. 152, New York,Macmillan, 1940.

Noller: Chemistry of Organic Compounds, 2nd ed., pp. 432-38,Philadelphia, Saunders, 1958.

NATALIE TROUSOF, Primary Examiner U.S. C1. X.R. 424-273

